Process of reacting aminoalkylated cellulosic textiles with 8-hydroxy-quinoline sulfonic acids and metals forming chelate rings and products thereof



United States Patent PROCESS OF REACTING AMINOALKYLATED CELLULOSIC TEXTILES WITH S-HYDROXY- QUINOLINE SULFONIC ACIDS AND MlETALS FORMING CHELATE RINGS AND PRODUCTS THEREOF Wilson A. Reeves and John D. Guthrie, New Orleans, La.,

assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Application April 10, 1953, Serial No. 348,136

12 Claims. (Cl. 8-129) (Granted under Title 35, U. S. Code (1952), see. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, for all governmental purposes, throughout the world, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to modified aminoalkylated cellulosic textiles such as slivers, yarns, threads and fabrics. More particularly, the invention provides aminoalkylated cellulosic textiles containing aryl chelate groups and such textiles to which rot resistance, ultraviolet fluorescence, and the like properties are imparted by metal atoms bound into chelate rings attached to the molecules of the textiles.

As herein employed, the term aminoalkylated cellulosic textile refers to a cellulosic textile in which alcoholic hydrogen atoms have been replaced by aminoalkyl radicals. Such textiles are characterized by a marked afiinity for acid dyestuffs and other valuable properties. Various processes of preparing aminoalkylated cellulosic textiles are known. U. S. 2,459,222 describes a particularly suitable process of preparing such textiles by reacting a cellulosic textile with Z-aminoethyl sulfuric acid in the presence of aqueous alkali. Aminopropylated textiles produced by reacting cellulosic textiles with 3- aminopropyl sulfuric acid by a similar procedure have similar chemical properties.

The aminoalkylated cellulosic textiles can suitably be employed in the present process in the form of slivers, yarns, threads, or fabric.

In general, the process of the present invention comprises reacting an aminoalkylated cellulosic textile with an aryl sulfonic acid containing chelate groups (i. e., Atomic groups capable of forming rings by one or two coordinate bonds, Hackhs Chemical Dictionary) dissolved in a dilute aqueous weak acid, until sulfonic acid salts of the amino groups of thetextile are formed.

The reaction produces novel chelate group-containing textiles which have physical properties comparable to the aminoalkylated cellulosic textiles from which they are produced. The chelate group-containing textiles also have the capacity of selectively removing polyvalent metals from aqueous solutions of salts of the metals and have numerous uses in addition to those known for aminoalkylated textiles.

Fluorescent textiles are produced in accordance with this invention, in general, by reacting the chelate groupcontaining textiles with metals that fluoresce when chelated. The reaction is preferably conducted by contacting the textile with an aqueous solution having a pH of from about 3 to 7 containing a soluble salt of the metal. Textiles which are both rot resistant and fluorescent are produced by contacting the chelate group-containing textiles with aqueous solutions of copper salts.

Fluorescent and/or rot resistant textiles produced in fabric from which it was produced.

accordance with this invention for acid dyes.

The dilute aqueous weak acid solutions of an aryl sulfonic acid containing a chelate group preferably contain enough of a water soluble acid, preferably a water soluble saturated fatty acid, such as formic, acetic or propionic acid, to make the water solution acetic and from about 0.5 to 5% of a water soluble aryl sulfonic acid containing one or more chelate groups.

Suitable aryl sulfonic acids comprise sulfonic acids which are soluble in water to the extent of at least 0.5 and which contain chelate groups capable of forming 5 or 6 membered rings by the attachment of a metal atom to members of groups such as imino, oxime, hydroxyl, or mercaptyl groups. Preferred sulfonic acids include 8-hydroxyquinoline-5-sulfonic acid, 8-hydroxyquinoline-4- sulfonic acid, and the like. 8-hydroxyquinoline-5-sultonic acid is particularly suitable.

The reaction between the aminoalkylated cellulosic textile and the aryl sulfonic acid can suitably be conducted at temperatures of from about 25 to 100 C. The reaction is preferably conducted at from 60 to C.

The reaction between the chelate group-containing textiles and a metal salt can suitably be conducted at temperatures of from about 25 to C. The reaction is preferably conducted at from about 40 to 80 C.

Suitable metal salts include zinc acetate, Zinc sulfate, copper acetate, copper sulfate, bismuth subnitrate, ferric chloride, and the like. The zinc and copper acetates are preferred.

Aqueous solutions of the metal salts preferably have a pH of from about 4 to 6.

The following examples are illustrative of the invention:

exhibit a marked afiinity Example 1 An aminoalkylated cellulosic textile was reacted with 8-hydroxyquinoline-5-sulfonic acid. The textile was immersed for about 15 minutes in a Water solution containing 1% of the sulfonic acid and 0.5% of acetic acid and maintained at about 70 C. The so reacted textile was washed free of reactants with water. The aminoalkylated textile used was a 48 by 48 cotton sheeting which had been aminoethylated to a nitrogen content of 0.8% by the process of Patent No. 2,459,222.

The chelate group-containing fabric produced by the reaction constituted a cellulosic textile in which alcoholic hydrogen atoms have been replaced by E-hydroxyquinoline-5-SO3H.HzNCHzCI-Iz-radicals. This fabric exhibited physical properties and an affinity for acid dyes co1nparaable'to the aminoalkylated fabric from which it was produced.

.A portion of .this chelate group-containing fabric was immersed for 2 minutes in a water solution containing 0.5% acetic acid and 5% copper acetate maintained at atemperature of 7075 C., removed, and washed free of the solution with water.

The copper-containing fabric so produced constituted a cellulosic textile in which alcoholic hydrogen atoms have been replaced by 8-hydroxyquinoline-5- SOsHHzNCHzCI-Iz-radicals in which the quinoline portion contains an atom of copper bound into a chelate ring. This fabric exhibited physical properties and an aflinity for acid dyes comparable to the aminoalkylated In ordinary light the fabric had a light green color, and. in ultraviolet light the fabric fluoresced to a deep wine red color.

A comparison of the rot resistance or mildew resistance of the fabric (determined by the soil burial test A. S. T. M. Standards, Philadelphia, 1951, pp. -1 and pp. 142 (D39-49); pp. 157-60 (D1l75-51T)) with untreated 48 x 48 cotton sheeting and aminoalkylated x tsbttan'hetingisi bmd in the following table:

Breaking strength (1b.) H

Example 2 e a sy n a n .f bri on ep edl r m aportion 9f, h ame Ph fie pl prcchta ni fa i by the. pr cl s nq c i mplc L sin antq u v l i t amount of Zinc etat l p qqbfth ome t e,- 4

Ihe zinc-containing fabric so produced constituted a icellulosic textile in which: aljcloholicfiy' drogen atoms have been repl ced h ..8-hyd yqu n line- 11: i Nc z zir c s inwh 9 theqi1 o nc po tion cqntains an atom of zinc bound into a chelate 51. .i i b x b d ph s ca -pr p rties.and an affinity for acid dye s co mparable to the aminoallgyl ated cellulosic textile from which it was produced Inordi- IY l th a c had a. l t y l w co r; andin ultraviolet light the fabric fluoresced to a bright yellow color.

Eicamp l'e 3 c A bismuth-containing fiber was prepared from apex: tion of the same chelate group-containing fabric byflthe process ofExample 1 using approximatelyan equivalent amount of bismuth subnitrate (BiONOaJ-IZO) in place of the copper acetate,

The bismuth-containing fabric so produced constituted a cellulosic textile in which alcoholic hydrogen atomshave been replaced by S-hydroxyquinoline-S- SOsH.H2NCI-I2CH2"-radicals m which the quinbl fl per: tion contains an atom of bismuth bound in a chelate ring. This fabric exhibited physical properties and affinity for acid dyes comparable to the amino'alkylate'di cellulosic textile from which it was produced, In nary light, the fabric had a yellow color, and" in ultra Violet light the fabric was red.

We claim:

1. A cellulosic textile in alcoholic hydr ogen atoms of the cellulosemolectiles have benreplac'e'd by 8-hydroxyquinoline -SO3H;H2NCH2CH2-radica1s. v H

2. A cellulo'sic textile in which alcoholiohydroge'n atoms of the cellulose molecules have been replaced by 8-hydroxyquinoline-5 -SO3H;HzNCHzC adijcals'hih which the'quinoline portion contains an atom 6r cd se'r bound into a chelate ring. A k p I 31 ,c'ellillosic t le n ,f h lq b i d en atoms or he cellulose moleculesflhave. been replaced by 8-hydroxyquinoline-5-SO3H.H2NCI-IzCH2 radicals in which the quinoline portion contains an atom of zinc bound into a chelate ring.

4. A cellulosic textile in which alcoholic hydrogen atoms of the cellulose molecules have been replaced by 8-hydroxyquinoline-5:SOsI-I.HzNCHzCHz-radicals in which the quinoli ne portion contains an atom of bismuth bound into achelate ring, A,, r M .5. A cellulosic textile in which: alcoholic hydrogen atbmspr the c'ellulos'emoleculeshave been replaced by 8-hydroxyquinoline-5-SO3H.H2NCH2CHg radicals in which the quinoline portion contains an atom of polyvalent metal bound into' achelate ring, said polyvalent metal being one which fiuoresces when so bound in a chelate ring.

6. A iprocessc comprising, -reacting an, amino-loweralkylated cellulosic textile. witha dilute aqueous weak acid solution of a rcompound from the group consisting of 8-hydroxyquinoliiie-5-sulfonic acid and 8-hydroxyquinolineA-Sulfonic, acid until amino groupseof the cellulosie textile are converted to sulfonic acid salts. h 7. A process comprising reacting an arping-loweralkylated eellul o'sjic textile with a dilute aqueous weak cids'olutipn of a bii uound fro the g' 91 P- q istin f. 8 d QXYQi I i -Sslflfimia ac and. sy r xyiiiimo 1ne-4-sulforiic acid until amino groups of the cellulpsic textile are conve ed to sulfo nic' a id salts, and iiii T tih' he te ti e pro uc d. ith-a l l Q 7 q u we a'cid solutionosa1t of polyyale'ntm al capable or forming fluoresce t c t r fleon a n n om:

offsaidt'ex a ,c .c 8. A cellu o's'ic textile in which alcoholic hydrogen atoms of the cellulose molecules haye heen replaced by, 8'.11""a r'" qq" CH2QH2-radi'cals1 ;in which. meta olit port n n ai sap at m a pelvnt'lmet'alfroin fllQglfOjUP consisting of c op'per, zinc, bismuth, and on bound into ache'late ring". .7

41. Atp p s nc i mr ri m rr c, an v2 111., :='r-. alkylated cellulosio textile with adilute] aqueQusweak acid solution of 8-hydroxyquinoline-i sulfonic acid, until amino g'roup's of the c elliulosie .1X ll are converted to sulfonici acid salts, and then reacting the textile so producedbwith dilute weak acid solution of a saltof a polyiialent vrnetalfrom the group consisting of copper, zinc, bismuth, and iron to produce a textile having metal atoms bound in chelate rings attached to the molecules of saidtextile. I a 1 ,9, r .v 10. The process of claim 9 in which the metal salt is copper acetate. t

11'. The process of claim 9 in which the metal salt is z'inc acetate, 4 v 12'. Thejprocss of claim 9 in which the metal salt is bismuth subnitrate. W A p l 7 References Cited in the file of this patent UNITED STATES PATENTS H Guthrie Jan. 18, 1949 

5. A CELLULOSIC TEXTILE IN WHICH ALCOHOLIC HYDROGEN ATOMS OF THE CELLULOSE MOLECULES HAVE BEEN REPLACED BY 8-HYDROXYQUINOLINE-5-SO3H.H2NCH2CH2-RADICALS IN WHICH THE QUINOLINE PORTION CONTAINS AN ATOM OF POLYVALENT METAL BOUND INTO A CHELATE RING, SAID POLYVALENT METAL BEING ONE WHICH FLUORESCES WHEN SO BOUND IN A CHELATE RING.
 7. A PROCESS COMPRISING REACTING AN AMINO-LOWERALKYLATED CELLULOSIC TEXTILE WITH A DILUTE AQUEOUS WEAK ACID SOLUTION OF A COMPOUND FROM THE GROUP CONSISTING OF 8-HYDROXYQUINOLINE-5-SULFONIC ACID AND 8-HYDROXYQUINOLINE-4-SULFONIC ACID UNTIL AMINO GROUPS OF THE CELLULOSIC TEXTILE ARE CONVERTED TO SULFONIC ACID SALTS, AND REACTING THE TEXTILE SO PRODUCED WITH A DILUTE AQUEOUS WEAK ACID SOLUTION OF A SALT OF POLYVALENT METAL CAPABLE OF FORMING FLUORESCENT CHELATE RING-CONTAINING COMPOUNDS TO PRODUCE A TEXTILE HAVING POLYVALENT METAL ATOMS BOUND IN CHELATE RINGS ATTACHED TO THE MOLECULES OF SAID TEXTILE. 